CN100569295C - With the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier - Google Patents

With the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier Download PDF

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Publication number
CN100569295C
CN100569295C CNB200610053174XA CN200610053174A CN100569295C CN 100569295 C CN100569295 C CN 100569295C CN B200610053174X A CNB200610053174X A CN B200610053174XA CN 200610053174 A CN200610053174 A CN 200610053174A CN 100569295 C CN100569295 C CN 100569295C
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vanadium
exchange resin
anion exchange
carrier
resin
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CN1927222A (en
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夏枚生
靳明建
胡彩虹
张红梅
熊莉
朱兴一
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of with the anion exchange resin be carrier vanadium replenishing agent and preparation method and purposes.It is a kind of anion exchange resin that contains active vanadium, and by weight percentage, the content of vanadium in anion exchange resin is 0.01~1.0%.Its preparation method is to utilize anion exchange resin can play the characteristics of exchange interaction with anion, and the vanadium anion is implanted in the anion exchange resin.Because ion exchange resin is a kind of control slow-released carrier of function admirable, the vanadium of institute's load had the control slow releasing function, thereby improved the absorption rate of vanadium greatly.Vanadium replenishing agent of the present invention has low toxicity, characteristics of high efficiency, can be used as to mend the vanadium feed additive; The health product and the medicine that also can be used for preparing human oral vanadium replenishing and treat human diseases by the vanadium of drug treatment.

Description

With the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier
Technical field
The present invention relates to the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier.
Background technology
Vanadium is a micro elements needed by human, its biological action more complicated, as influence myocardial contraction, stimulate some cell division, antitumaous effect and toxic action etc.Up to now, the most attractive effect is its ILA in the biological action of vanadium.In a large amount of whole and stripped zooperies.Confirmed that vanadate has ILA.Vanadium does not influence insulin secretion, but can strengthen the sensitivity of tissue to insulin.Its mechanism of action still imperfectly understands.But many scholars think that it may work by some link behind Insulin receptor INSR or the receptor and the biological alternative pathway of non-insulin-dependent.To insulin insensitivity or when malfunctioning, vanadate can also play antidiabetic effect effectively.Vanadate can improve the abnormal metabolism state of diabetes rat, also can recover diabetes rat pyruvate kinase activity, and this is one of mechanism of vanadate ILA.Drink vanadic acid sodium and can make blood glucose in diabetic rats recover normal, the minimum effective dose of vanadic acid sodium is 100mg/L.If the dosage of vanadic acid sodium is reduced to below the 80mg/L, then there is not obvious hypoglycemic activity.The prompting vanadium must reach its ILA of finite concentration competence exertion in vivo.Inorganic vanadium performance ILA must reach suitable dosage, and high concentration easily causes nausea,vomiting,diarrhea, liver toxicity even death; Present many scholars mostly are devoted to the chemical compound research and development of vanadium, developed organic vanadium in succession, as join wheat and cross vanadyl salt (bis-maltolato oxovanadate, BMOV), vanadyl pentanedione salt (Vanadyl acetylacetonate, VAc), vanadyl 3-ethyl pentanedione salt (Vanadyl 3-ethyl-acetylacetonate, VEt) etc., but organic vanadium still needs drug administration by injection, and research just has been in the starting stage, clinically sees Related product far away.
Ion exchange resin (Ion exchange resin, IER) be the cancellated macromolecular compound that a class has functional group, its structure is made up of three parts: insoluble three dimensions mesh skeleton, be connected functional group on the skeleton and functional group with the exchangeable ion of opposite charges.According to the different in kind of cation exchange groups, ion exchange resin is divided into six big classes: storng-acid cation exchange resin, weak-acid cation-exchange resin, strong alkalinity anion literary composition change resin, weak-base anion-exchange resin, sequestration ion exchange resin, amphoteric ion-exchange resin, oxidation-reduction quality ion exchange resin.According to resin with tradable ionic nature, ion exchange resin is divided into cation exchange resin and anion exchange resin substantially, has acid function base (highly acid: sulfonic group (SO 3H); Faintly acid: carboxylic acid group (COOH), phosphate (PO 3H 2) etc.), the polymer that can exchange with cation is cation exchange resin; Have alkaline functional base (strong basicity: quaternary ammonium group-N (CH 3) 3Deng; Alkalescence: the primary, the second month in a season, tertiary amine groups (CH 2NH 2,--CH 2NHR ,-CH 2NR 2) etc.), the polymer that can exchange with anion is anion exchange resin.
According to the difference of resin physical arrangement, can be divided into gel-type and macroporous ion-exchange resin two big classes to ion exchange resin again.Gel type resin is the ion exchange resin of the homogeneous phase high-molecular gel structure of a class appearance transparent, the interior mutually micropore that produces of suction back resin, and counter ion can diffuse into and carry out ion exchange in the micropore that is produced by suction.The basic characteristics of macroreticular ion exchange resin be do in whole resin inside, wet or contraction, swelling all exist the duct more, bigger than general gel-type in water, thereby surface area is big, in ion exchange process, the easy diffusion mobility of ion, exchange velocity is very fast.
Full name of ion exchange resin claims to be rearranged by specific name, skeleton (or group) title, basic designation.The model name of ion exchange resin is different and fixed according to structure, form by three Arabic numerals: the classification of the first bit digital representative products, second-order digit is represented the difference of framing structure, and the 3rd bit digital is a serial number, in order to difference group, cross-linking agent etc.All macroreticular ion exchange resins add before model, and-D represents: gel-type ion-exchange resin connects Arabic numerals with " * " and represents after model.Wherein, classification designator has 0,1,2,3,4,5,6, corresponding representative strong-acid type, weak-type, strong base, weak base type, chelating type, both sexes and oxidation-reduction ion-exchange resin.The skeleton code name has 0,1, and 2,3 etc., represent polystyrene, acrylic acid series, phenolic aldehyde system, epoxy system etc. respectively.
Separation and purification pure water preparation that ion exchange resin is applied to analytical chemistry medicine for a long time reach fields such as being used for the environmental conservation blood purification in the recent period.Since proposing ion exchange resin first in 1956 and being used to delay drug release as pharmaceutical carrier, the report that utilizes ion exchange technique to delay drug release constantly increases, and has entered the practicality stage.Ion exchange resin has multiple good characteristic as pharmaceutical carrier, at present its controlled release, transdermal administration, site-specific delivery of drugs, instant, iontophoresis transdermal, nasal cavity, topical and cover side such as bitter taste of drug and application very deep research is all arranged, some product goes on the market.Ion exchange resin is control drug release in gastrointestinal tract mainly, be ion exchange resin controlled-release administrating system (Ion-Exchange ResinControlled Drag Delivery System, IERCDDS), compare with other drug-supplying systems, the main feature of IERCDDS is the volume that the release of medicine does not rely on pH value, enzymatic activity, temperature and gastrointestinal fluid in the gastrointestinal tract, because ionic species and strength maintenance thereof in the gastrointestinal fluid are constant relatively, so medicine can constant rate of speed discharge in vivo.
Summary of the invention
The purpose of this invention is to provide with the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier.
The vanadium replenishing agent that with the anion exchange resin is carrier is a kind of anion exchange resin that contains active vanadium, and by weight percentage, the content of vanadium in anion exchange resin is 0.01~1.0%.。
With the anion exchange resin is the preparation method of the vanadium replenishing agent of carrier, may further comprise the steps:
1) anion exchange resin is placed 0.5~2mol/L hydrochloric acid solution of 1~2 times of resin volume soaked 2~5 hours, drain after the acid solution with water rinse to neutral, 0.5~2mol/L sodium hydroxide solution with 1~2 times of resin volume soaked 3~6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) is packed in the exchange column, vanadium content is the vanadic salts of anion exchange resin weight 0.01~1.0%, is pre-configured to 0.1~1% aqueous solution, and by exchange column, room temperature reaction 2~5 hours is washed 2~4 times with the flow velocity of 1~10mL/min;
3) with step 2) anion exchange resin of gained load vanadium is being lower than 70 ℃ of oven dry down, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier.
The vanadic salts that uses in the invention is positive vanadate, metavanadate or pyrovanadate.
The vanadium replenishing agent that with the anion exchange resin is carrier is mended the vanadium feed additive as cattle, sheep, poultry, aquatic animal.With the anion exchange resin health product and the medicine that the vanadium replenishing agent of carrier is used to prepare human oral vanadium replenishing and treats human diseases by the vanadium of drug treatment.
Advantage of the present invention is:
(1) utilize anion exchange resin can play the characteristics of exchange interaction with anion, the vanadium anion is implanted in the anion exchange resin, implementation method is easy, suitability for industrialized production, and cost is lower.
(2) because ion exchange resin is a kind of control slow-released carrier of function admirable, the vanadium of institute's load is had the control slow releasing function, thereby improved the absorption rate of vanadium greatly.
(3) of the present invention is that the vanadium replenishing agent of carrier has low toxicity, characteristics of high efficiency with the anion exchange resin, can be used as and mends the vanadium feed additive; The health product and the medicine that also can be used for preparing human oral vanadium replenishing and treat human diseases by the vanadium of drug treatment.
The specific embodiment
Anion exchange resin is strong-base anion-exchange resin or weak-base anion-exchange resin, has the alkaline functional base, comprises strong basicity (quaternary ammonium group-N (CH 3) 3) and alkalescence (primary, secondary, tertiary amine groups ,-CH 2NH 2,--CH 2NHR ,-CH 2NR 2) functional group.According to the difference of anion exchange resin physical arrangement, can be gel-type or macroporous ion-exchange resin.The anion exchange resin skeleton is polystyrene or acrylic acid series.
Embodiment 1
1) (this product is equivalent to the U.S.: AmberliteIRA-400 with 201 * 7 commercially available strong-basicity styrene series anion exchange resins, West Germany: LewatitM500, Japan: DiaionSA-10A), place the 0.5mol/L hydrochloric acid solution of 1 times of resin volume to soak 2 hours, drain after the acid solution with water rinse to neutral, 0.5mol/L sodium hydroxide solution with 1 times of resin volume soaked 3 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the sodium vanadate of anion exchange resin weight 0.01% with vanadium content, is configured to 0.1% vanadic salts aqueous solution, and by exchange column, room temperature reaction 2 hours is washed 2 times with the flow velocity of 1mL/min;
3) with step 2) anion exchange resin of gained load vanadium is being lower than 70 ℃ of oven dry down, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier.By weight percentage, the content of vanadium in anion exchange resin is 0.01%.
Embodiment 2
1) (this product is equivalent to the U.S.: AmberliteIRA402 with commercially available 201 * semi-finals basicity styrene series anion exchange resin, Germany: Lewatit M504MB), place the 2mol/L hydrochloric acid solution of 2 times of resinites to soak 5 hours, drain after the acid solution with water rinse to neutral, 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the sodium metavanadate of anion exchange resin weight 1.0% with vanadium content, is configured to 1% vanadic salts aqueous solution, and by exchange column, room temperature reaction 5 hours is washed 4 times with the flow velocity of 10mL/min;
3) with step 2) anion exchange resin of gained load vanadium is being lower than 70 ℃ of oven dry down, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier.By weight percentage, the content of vanadium in anion exchange resin is 1.0%.
Embodiment 3
1) (this product is equivalent to the U.S.: AmberliteIRA-68 with commercially available D311 macroreticular weakly base acrylic acid type anion exchange resin; Germany: AP-49), place the 1mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, the 1mol/L sodium hydroxide solution with 1.5 times of resin volumes soaked 5 hours then, drained behind the alkali liquor with water rinse to neutral;
2) be the sodium pyrovanadate of anion exchange resin weight 0.05% with vanadium content, be configured to 0.5% vanadic salts aqueous solution, add in the resin of step 1) room temperature reaction 5 hours in stirring down;
3) reactant liquor washing step 2) 4 times, filtering means dehydration;
4) filter cake with the step 3) gained is being lower than 70 ℃ of oven dry down, is pulverizing, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier.By weight percentage, the content of vanadium in anion exchange resin is 0.05%.
Embodiment 4
1) with commercially available D201 macroporous strong basic styrene series anion exchange resin (the suitable U.S. of this product: AmberliteIRA-900, West Germany: Lewatit MP-500, Japan: Diaion308), place the 0.5mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 4 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the positive potassium vanadate of anion exchange resin weight 0.5% with vanadium content, is configured to 0.8% vanadic salts aqueous solution, and by exchange column, room temperature reaction 4 hours is washed 3 times with the flow velocity of 5mL/min;
3) with step 2) anion exchange resin of gained load vanadium is being lower than 70 ℃ of oven dry down, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier.By weight percentage, the content of vanadium in anion exchange resin is 0.5%.

Claims (3)

1. one kind is the vanadium replenishing agent of carrier with the anion exchange resin, it is characterized in that, it is a kind of anion exchange resin that contains positive vanadate, metavanadate or pyrovanadate, and by weight percentage, the content of vanadium in anion exchange resin is 0.01~1.0%.
One kind as claimed in claim 1 be the preparation method of the vanadium replenishing agent of carrier with the anion exchange resin, it is characterized in that the step of method is as follows:
1) anion exchange resin is placed 0.5~2mol/L hydrochloric acid solution of 1~2 times of resin volume soaked 2~5 hours, drain after the acid solution with water rinse to neutral, 0.5~2mol/L sodium hydroxide solution with 1~2 times of resin volume soaked 3~6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) is packed in the exchange column, vanadium content is the vanadic salts of anion exchange resin weight 0.01~1.0%, is pre-configured to 0.1~1% aqueous solution, and by exchange column, room temperature reaction 2~5 hours is washed 2~4 times with the flow velocity of 1~10mL/min;
3) with step 2) anion exchange resin of gained load vanadium is being lower than 70 ℃ of oven dry down, and obtaining with the anion exchange resin is the vanadium replenishing agent of carrier;
Said vanadic salts is positive vanadate, metavanadate or pyrovanadate.
One kind as claimed in claim 1 be the purposes of the vanadium replenishing agent of carrier with the anion exchange resin, it is characterized in that health product and medicine that it is used to prepare human oral vanadium replenishing and treats human diseases by the vanadium of drug treatment.
CNB200610053174XA 2006-08-28 2006-08-28 With the anion exchange resin is vanadium replenishing agent and the preparation method and the purposes of carrier Expired - Fee Related CN100569295C (en)

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